Lubricants



Patented Mar. 27, 1951 LUBRICANTS Clarence M. Loane and Lawson VJ. Mixon, Hammond, ind, assignors to Standard Oil Company, Chicago, 111., a corporation of Endiana Jo Drawing. Application August 8, 1947, Serial No. 767,656

11 Claims.

This invention relates to improvements in lubricants and more particularly to hydrocarbon oil compositions which are non-corrosive and resistant to oxidative deterioration. More particularly, the present invention is directed to internal combustion engine lubricants which are resistant to the formation of gums, resinous and varnish-like materials and which are non-corrosive to metal surfaces, especially bearings of the hard metal alloy type.

This application is a continuation-in-part of our copending application Serial No. 568,935, filed December 19, 1944, now abandoned.

Many oils ar not well suited as lubricants for use in internal combustion engines, particularly those of the type operating under severe conditions, since under such severe operating conditions the oils are susceptible to oxidative deterioration, resulting in the development of carbonaceous and/or resinous or similar varnish-like deposits in the engine and on and about the valves and rings of the engine. Furthermore, such lubricants often develop products of oxidative deterioration which are corrosive, particularly to the bearings of the hard metal alloy type, such as copper-lead bearings, cadmium-silver bearings, etc., which are frequently used in such'engines.

It has heretofore been discovered that certain reaction products of a phosphorus sulfide and a hydrocarbon, particularly an olefin or an olefin polymer, when added in small amounts to a hydrocarbon oil, such as a mineral oil, are effective in inhibiting the formation of varnish, sludge, carbon and the like in lubricating oils during use. However, it has since been found that under certain conditions lubricants containing these reaction products of a phosphorus sulfide and a hydrocarbon and particularly the neutralized reaction products do not effectively inhibit the formation of sludge, varnish, and other resinous materials in the engine. The use of the neutralized reaction products of a phosphorus sulfide and a hydrocarbon in lubricants is the subject matter of United States Patent No. 2,316,082 issued to C. M. Loane and J. W. Gaynor April 6, 194.3. The use of small amounts of an organic sulfur compound or elemental sulfur in combination with the neutralized reaction products of a phosphorus sulfide and a hydrocarbon in lubricants to inhibit the corrosive action of oxidative deterioration products is the subject matter of United States Patent 2,316,090 issued to C. D. Kelso and L. W. Mixon on April 6, 1943. While the organic sulfur compounds or elemental sulfur, in combination with the neutralized reaction products of a phosphorus sulfide and a hydrocarbon, in lubricants effectively inhibit corrosion, such lubricants under certain conditions are not effectively inhibited against the formation of resinous or other varnish-like dedeterioration and which will render such oils non-corrosive. It is another object of the inventionto provide lubricants for internal combustion engines which do not form carbonaceous deposits or resinous varnish-like materials on and about the valves, pistons and rings of such engines and which are not corrosive to metals, particularly to hard alloy bearing metals of the copper-lead and cadmium-silver type.

In accordance with the present invention the foregoing objects can be attained by adding to oils, such as hydrocarbon oils, for example mineral lubricating oils, small amounts of the neutralized reaction products of a phosphorus sulfide and a hydrocarbon and small amounts of certain metal sulfonates, particulrly salts of preferentially oilsoluble, sulfonated, olefin polymer-alkylated aromatic compounds and olefin polymer sulfonates. The neutralized phosphorus sulfide-hydrocarbon reaction products can be employed in amounts within the range of from about 0.001% to about 10%, and preferably from about 0.01% to about 3%; and metal sulfonates, particularly the oil-soluble salts of the olefin polymer-alkylated aromatic sulfonates and the oil-soluble salts of olefin polymer sulfonates, can be employed in combination with the neutralized phosphorus sulfide-hydrocarbon reaction products in amounts from about 0.01% to about 10%, and preferably from about 0.1% to about 3%. In addition, the lubricant composition may contain from about 0.001% to about 5%, of av corrosion inhibitor such as elemental sulfur or other organic sulfur compounds, such as sulfurized mineral oil, sulfurized olefin polymers, or a sulfurized terpene. Furthermore, the lubricant may contain from 0.01% to 1% of conventional inhibitors, such as aromatic amines and phenolic compounds.

It is also within the contemplation of this invention to provide the combination of addition agents, herein-described, in the form of a concentrate in a suitable oil base, the concentrate containing from about 10% to about 50% or more of the additives. Such concentrates are used for blending with a hydrocarbon oil or other oils in the proportions desired for the particular condi- 3 tions of use. Convenient1y,'a concentrated solution of an oil containing more than 2% by weight, based on the oil, of the neutralized reaction product of a phosphorus sulfide and a hydrocarbon and more than by weight, based on the oil, of a metal sulfonate can be prepared so that upon further dilution with the oil, such as a hydrocarbon lubricating oil, a homogeneous mixture can be obtained containing from about 0.001% to about 10% of the neutralized reaction product of a phosphorus sulfide and a hydrocarbon and from about 0.01% to about 10% of the metal sulfonate.

As aforesaid, one of the components of the improved lubricant is the neutralized reaction product of a hydrocarbon and a phosphorus sulfide such as P283, PiSz, P437, or other phosphorus sulfides, and preferably phosphorus pentasulfide, P2535. The hydrocarbon constituent of this reaction is preferably a mono-olefin hydrocarbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or isomono-olefin hydrocarbons such as propylenes, butylenes, and amylenes or the copolymers obtainedby the polymerization of hydrocarbon mixtures containing isomono-olefins and monoolefins of less than 6 carbon atoms. The polymers may be obtained by the polymerization of these olefins or mixtures of olefins in the presence of a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts pe- The polymers employed are preferably monoolefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at a temperature of from about 80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel-Crafts typesuch as, for example, boron fluoride, aluminum chloride and the like. In the preparation of these polymers We may employ, for example, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline.

A suitable polymer for the reaction with phosphorus sulfide is the product obtained by polymerizing in the liquid phase a hydrocarbon mixture containing butylenes and isobutylenes together with butanes and some C3 and C5 hydrocarbons at a temperature between about 0 F. and 30 F. in the presence of aluminum chloride. A suitable method for carrying out the polymerization is to introduce the aluminum chloride into the reactor and introduce the hydrocarbon mixture cooled to a temperature of about 0 F. into the bottom of the reactor and pass it upwardly through the catalyst layer while regulating the temperature within the reactor so that the polymer product leaving the top of the reactor is at a temperature of about 30 F. After separating the polymer from the catalyst sludge and unreacted hydrocarbon, the polymer is fractionated to obtain a fraction of the desired viscosity such as, for example, from about 80 seconds to about 2000 seconds Saybolt Universal at 210 F.

Another suitable polymer is that obtained by siu polymerizing in the liquid phase a hydrocarbon mixture comprising substantially C3 hydrocarbons in the presence of an aluminum chloridecomplex catalyst. The catalystis preferably prepared by heating aluminum chloride with isoootane. The hydrocarbon mixture is introduced into the bottom of the reactor and passed upwardly through the catalyst layer, While a temperature of from about 50 F. to about 110 F. is maintained in the reactor. The propane and other saturated gases pass through the catalyst, while the propylene is polymerized under these conditions. The propylene polymer can be fractionated to any desired molecular weight, pref erably from about 500 to about 1000 or higher.

Other suitable polymers can be obtained by polymerizing a hydrocarbon mixture containing about 10% to about 25% isobutylene at a temperature of from about 0 F. to about F. and preferably 0 F. to about 32 F. in the presence of boron fluoride. After the polymerization of the isobutylene together with a relatively minor amount of the normal olefins present, the reaction mass is neutralized, Washed free of acidic substances and the unreacted hydrocarbons subsequently separated from the polymers by distillation. The polymer mixture so obtained, depending upon the temperature of reaction, varies in consistency from a light liquid to viscous, oily material and contains polymers having molecular weights ranging from about 100 to about 2000 or higher. The polymers so obtained may be used as such, or the polymer may be fractionated under reduced pressure into fractions of increasing molecular weights, and suitable fractions reacted with the phosphorus sulfide to obtain the desired reaction products. The bottoms resulting from the fractionation of the polymer may have Saybolt Universal viscosities at 210 F. ranging from 50 seconds to about 10,000 seconds and are zvell suited for the purpose of the present inven- Essentially parafiinic hydrocarbons such as bright stock residuums, lubricating oil distillates, petrolatums, or paraiiin waxes may be used. There can also be employed the condensation products of any of the foregoing hydrocarbons, usually through first halogenating the hydrocarbons with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride and the like.

Examples of high molecular weight olefinic hydrocarbons which can be employed as reactants are cetene (C16), cerotene (C26), melene (C30) and mixed high molecular alkenes obtained by cracking petroleum oils.

Other preferred olefins suitable for the preparation of the herein-described phosphorus sulfide reaction'products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins can be obtained by the dehydrogenation of paraffms, such as by the cracking of parafiin waxes, or by the dehydrohalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parafiin waxes.

-The olefins obtained by dehydrohalogenation of long chain alkyl halides are preferably those obtained by dehydrohalogenation of monohalogenated waxes, such as for example, those obtained by dehydrochlorination of monochlor parafiin wax. The alkyl halides are decomposed to yield olefins according to the reaction in which n is a whole number, preferably 20 or more, and X is a halogen. It is preferred to employ paraffin waxes having at least about 20 carbon atoms per molecule, and melting points upwards from about 90 F. to about 140 F.

To obtain the halogenated paraffin wax, for example, chlorinated paraffin wax, chlorine is introduced into the wax, maintained in a molten state, until the wax has a chlorine content of from about 8% to about 15%. The chlorinated wax product is a mixture of unchlorinated wax, monochlor wax and polychlor wax. This chlorinated product may be used as such, but it is advantageous to use the substantially monochlor wax fraction. The monochlor wax fraction can be segregated from the unchlorinated wax and the polychlor wax fractions by taking advantage of the differences in the melting points of the various fractions, since the melting point of the wax varies with the extent of chlorination, i. e. the melting point of the unchlorinated wax is greater than that of the monochlor wax, and the melting point of the latter is greater than that of the polychlor wax. Thus, the monochlor paraffin wax can be separated from the unchlorinated and the polychlor wax ractions by means such as sweating,,fractional distillation, solvent extraction, solvent precipitation, and fractional crystallization.

The high molecular weight olefins are obtained by removing the halogen as hydrogen halide from the halogenated parafiin wax. For example, the corresponding olefin is obtained from the monochlor parafiin wax by removing the chlorine from the latter as hydrogen chloride. The monochlor wax can be dehydrochlorinated by heating to a temperature of from about 200 F. to about 600 F. in the presence of a dehydrochlorinating. agent such as an alkali metal hydroxide or an alkaline earth metal hydroxide or oxide. Other alkaline inorganic or organic materials can also be used. The chlorine can also be removed from the chlorowax by heating the same for a prolonged period in the absence of any dehydroohlorinating agent. After the dehydrohalogenation has been completed the olefin so obtained can be further purified by removing the dehydrohalogenating agent by means of filtration or by other suitable means.

As other starting materials there can be used the polymer or synthetic lubricating oil obtained by polymerizing unsaturated hydrocarbons, resulting from the vapor phase cracking of paraffin waxes, in the presence of aluminum chloride, which isfully described in United States Patents Nos. 1,995,260, 1,970,002 and 2,091,398. Still another type of olefin polymer which may be employed is the polymer resulting from the treatment of vapor phase cracked gasoline and/or gasoline fractions with sulfuric acid or solid absorbents such as fullers earth whereby unsaturated polymerized hydrocarbons are removed. Also contemplated within the scope of this invention is the treatment with phosphorus sulfide of the polymers resulting from the voltolization of hydrocarbons as described, for example in United States Patents Nos. 2,197,768 and 2,191,787.

Also contemplated within the scope of the present invention are the reaction products of a phosphorus sulfide with an aromatic hydrocarbon such as for example benzene, naphthalene, toluene, xylene, diphenyl and the like, or with an alkylated aromatic hydrocarbon such as for example, benzene having an alkyl substituent having at least four carbon atoms and preferably at least eight carbon atoms such as for example, long chain parafiln waxes, olefin pol mers and the like.

The phosphorus sulfide-hydrocarbon reaction product can be readily obtained by reacting a phosphorus sulfide, for example P285 with the hydrocarbon at a temperature of from about 200 F. to about 500 F. and preferably from about 200 F. to about 400 F., using from about 1% to about 50% and preferably from about 5% to about 25% of the phosphorus sulfide in the reaction. It is advantageous to maintain a nonoxidizing atmosphere such as for example, an atmosphere of nitrogen above the reaction mixture. Usually it is preferable to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification becomes necessary; however, an excess amount of phosphorus sulfide can be used and separated from the product b filtration or by dilution with'a solvent such as hexane, filtering and subsequently removing the solvent by suitable means such as by distillation. If desired, the reaction product can be further treated with an agent having an active hydrogen atom such as steam at an elevated temperature of from about F. to about 600 F.

The phosphorus sulfide-hydrocarbon reaction roduct normally shows a titratable acidity which is neutralized by treatment with a basic reagent. The phosphorus sulfide-hydrocarbon reaction roduct when neutralized with a basic reagent containing a metal constituent is characterized by the presence or retention of the metal constituent of the basic reagent. Other metal constituents such as a heavy metal constituent can be introduced into the neutralized product by reacting the same with a salt of the desired heavy metal.

The term neutralized phosphorus sulfide-hydrooarbon reaction product as used herein means a phosphorus sulfide-hydrocarbon reaction product having at least about 1% of its titratable acidity neutralized by reaction with a basic reagent and includes the neutralized phosphorus sulfide-hydrocarbon reaction products containing a metal constituent resulting from said neutralization or resulting from the reaction of a heavy metal salt with the phosphorus sulfide-hydrocarbon reaction product treated with a basic reagent.

The neutralized phosphorus sulfide-hydrocarbon reaction product can be obtained by treating the reaction product with a suitable basic compound such as a hydroxide, carbonate, oxide or sulfide of an alkaline earth metal or an alkali metal such as, for example, potassium hydroxide, sodium hydroxide, sodium sulfide, etc.

Other basic reagents can be used such as for example, ammonia or an alkyl or aryl substituted ammonia such as amines. The neutralization of the phosphorus sulfide-hydrocarbon reaction product is carried out preferably in a non-oxidizing atmosphere by contacting the reaction product either as such or dissolved in a suitable solvent such as naphtha with a solution of the basic reagent, for example, potassium hydroxide or sodium hydroxide dissolved in alcohol. As an alternative method, the reaction product can be treated with solid alkaline compounds such as KOH, NaOH, NazCOs, K2003, CaO, NazS, and the like at an elevated temperature of from about 100 F. to about 600 F. As was aforesaid, when the phosphorus sulfide-hydrocarbon reac-. tion product is neutralized with a basic reagent containing a metal constituent, the neutralized reaction product is characterized by the presence of the metal constituent of the basic reagent. Neutralized reaction products containing a heavy metal constituent such as, for example, tin, titanium, aluminum, chromium, cobalt, zinc, iron, and the like, can be obtained by reacting a salt of the desired heavy metal with the phosphorus sulfide-hydrocarbon reaction product which has been treated with a basic reagent. It will be understood that when the neutralization is accomplished with a polyvalent basic material such as lime, a product having excess basicity may be obtained.

The sulfonates which are used in combination with the neutralized reaction products of a phosphorus sulfide and a hydrocarbon are preferentially oil-soluble products obtained by sulfonating an olefin polymer of the following type or by alkylating an aromatic hydrocarbon with an olefin polymer having a molecular weight within the range of from about 100 to about 5090, or higher, and sulfonating the alkylated aromatic hydrocarbon with a suitable sulfonating agent such as, for example, sulfuric acid, although other sulfonating agents can be used. The olefin polymers which are sulfonated or which are used for the alkylation of the aromatic are preferably mono-olefin polymers such as for example, polybutenes, polypropylenes, polyamylenes and the like which can be prepared by polymerizin low molecular weight mono-olefinic hydrocarbons or isc-mone-olefinic hydrocarbons such as propylene, butylene and amylenes, or copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and monoolefins. Polymerization can suitably be carried out in the presence of a catalyst such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other halide catalysts of the Friedel- Crafts type in the manner hereinbefore described. In addition to such polymers the alkylating agent may be cracked wax polymers.

The aromatic nucleus which is alkylated can be a monocyclic or polycyclic aromatic compound such as, for example, benzene, toluene, xylenes, cumene, naphthalene, methyl naphthalenes, ethyl naphthalenes, isopropyl or other alkyl naphthalenes, cliphenyl, alkyl d'iphenyls, anthracene, alkyl anthracenes and the like. The aromatic nucleus can contain in addition to hydrocarbon substituents other substituents such as for example, halogen, nitro, hydroxy or other substituent groups.

The sulfonation of the alkylated aromatic compound can be carried out with any suitable sulfonating agent, such as, for example sulfuric acids of various strengths such as sulfuric acids from about 88% strength to fuming sulfuric acid. The temperature at which the sulfonation is carried out can be varied within wide limits; for example, temperatures as low as 2G F. and as high as 200 F. can be employed, although temperatures within the range of about 1". to about 100 F. are generally preferred. The salts of the alkylated aromatic sulfonic acids so obtained can be prepared by neutralizing the acids with suitable neutralizing agents such as sodium or potassium hydroxide and the heavy metal salts thereof obtained by double decomposition with 8 the desired heavy metal salt. The sodium, potassium, calcium, barium, zinc, tin, lead, copper, cobalt, nickel, aluminum, titanium, magnesium, strontium, maganese, iron, lithium, cerium, rubidium, cesium, tungsten, vanadium salts of the oil-soluble sulfonated polymer alkylated aromatics or of the oil-soluble sulfonated polymers can suitably be employed.

The preparation of the preferentially oilsoluble alkyl aryl sulfonates is illustrated by the following example:

Two mols of a propylene polymer having a molecular weight of about 638 and four mols of benzene were stirred in an ice bath with fifteen grams of A1013 for three hours. An additional fifteen grams of A1Cl3 were added to the mixture, the ice bath removed and the mixture stirred for six hours. At the end of this time water was added to the reaction mass, and the polymer extracted with hexane, and the extract freed of hexane by evaporation.

The polymer alkylated benzene was sulfonated by reacting the same with IOU/2% H2604 in an amount to yield 1 equivalent dissolved S03 per equivalent of phenyl, the acid being added slowly to keep the temperature of the reaction mixture below F. An equivalent volume of hexane was added, the sludge settled and withdrawn. The sulfonic acid was then neutralized with dilute alcoholic KOH, the neutralized product diluted to 50% volume with a light oil (SAE 10), heated to 400 F. and filtered.

Similarly, butylene polymer alkylated benzene can be sulfonated.

The olefin polymers, e. g. propylene polymers and butylene polymers can be sulfonated by reacting the polymer with a strong sulfonating agent such as for example, concentrated or fuming sulfuric acid, chloro-sulfonic acid, etc. in the presence of an anhydride or chloride such as acetic anhydride, acetyl chloride, lactic anhydride, etc.

If desired, mixtures of the polymer alkylated aromatic sulfonates and the polymer sulfonates can be used in combination with the phosphorus sulfide-hydrocarbon reaction products.

The specific activity of the various hereinname-d metal sulfonates varies to some extent, all. of them, however, being effective varnish inhibitors.

The effectiveness of small amounts of the oilsoluble polymer alkylated aromatic sulfonates and olefin polymer sulfonates in inhibiting oxidation and the formation of varnish and resinous-like deposits in internal combustion engines when used in combination with the neutralized phosphorus sulfide-hydrocarbon reaction products is illustrated by the data presented in Table I. These data were obtained in the so-called 36 hour Chevrolet test made in accordance with the Cooperative Research Council Test Procedure, CRC Designation L-4 243 of February, 1943. This test is made in a six cylinder, spark ignition internal combustion engine equipped with copper-l ad alloy bearings and operating at 3150 R. P. M. with an oil temperature of 286 F. In this test the engine is dismantled at the end of the 36 hour running period and the amount of varnish deposited upon the pistons determined. Depending upon the amount of varnish formed, the piston is given a varnish rating of from 1 to 10; a badly varnish-coated piston is rated 1, a substantially clean piston is rated 10, and intermediate varnish-coated pistons are given corresponding intermediate ratings. In

addition the viscosity and acidity of each used oil sample were determined. The acidity was determined by weighing five grams of the oil into a 250 cubic centimeter flask, adding 20 cubic centimeters of neutralized naphtha and dissolving the oil therein by agitation. Forty cubic centimeters of a neutralized, saturated aqueous solution of sodium chloride and 40 cubic centimeters of neutralized 95% ethyl alcohol are then added to the flask and the contents boiled for one minute. Phenolphthalein is added to the solution and the oil titrated hot with 0.1N alkali, when the pink color is not rapidly discharged by swirling, the flask is shaken. The titration is continued until a definite pink color persists for 30 seconds after seconds of vigorous shaking. The acidity is expressed as milligrams of KOH per gram of oil.

The following oils were tested by this method:

A. A refined M. C. SAE 30 motor oil+0.75% of a KOH neutralized reaction product of P235 and a butylene polymer of about 1000 molecular weight.

B. A refined M. C. SAE 30 motor oil+1.5% of a KOI-I neutralized reaction product of P285 and a butylene polymer of about 1000 molecular weight.

C. A refined M. C. SAE 30 motor oil+1.0% of an oil-soluble potassium salt of propylene polymer alkylated benzene sulfonate.

D. A refined M. C. SAE 30 motor oil+2.0% of an oil-soluble potassium salt of propylene polymer alkylated benzene sulfonate.

E. Oil A+0.5% of the oil-soluble potassium:

salt of propylene polymer sulfonate.

F. Oil A+0.5% of the oil-soluble potassium salt of propylene polymer 1 sulfonate.

G. Oil A+1% sodium mahogany soap.

alkylated benzene Universal Saybolt at 100 F. T Milligrams KOH per gram of oil sample.

The above data clearly demonstrate the effectiveness of the combination of the neutralized phosphorus sulfide-hydrocarbon reaction product and the polymer alkylatecl aromatic sulionate and the polymer sulfonate of the present invention. The data also demonstrate the superiority of the additives of the present invention (samples E and F) over the oil-soluble petroleum sulfonates, i. e. mahogany soaps (samples G and H).

In addition to the foregoing additives, other additives, such as pour point depressors, antioxidants, metal deactivators, anti-rust agents, corrosion inhibitors, V. I. improvers, extreme pressure agents, and the like may be present in the lubricant com osition.

While We have described our invention as applied to lubricating oils, we contemplate the use of the combination of the herein described addn 1 Molecular Weight of polymer about 630.

tives in products other than lubricating oils, such as, for example, fuel oils, insulating oils, Waxes, greases, synthetic oils, non-drying animal and Vegetable oils and the like.

Percentages expressed herein and in the appended claims are weight percentages.

While We have described our invention by reference to specific preferred embodiments thereof, the invention is not to be considered as limited thereto but includes within its scope such modifications as come within the spirit of the appended claims.

We claim:

1. A non-aqueous lubricant composition comprising a major proportion of a hydrocarbon oil and in combination therewith from about 0.001% to about 10% of a potassium-containing neutralized reaction product of P285 and an olefin polyme! having a molecular weight of from about 500 to about 10,000 obtained by reacting said olefin polymer with from about 1% to about 50% P285 at a temperature of from about 200 F. to about 500 F. and neutralizing the resultant reaction product with a potassium-containing basic reagent, and from about 0.01% to about 10% of a potassium salt of a propylene polymer alkylated benzene sulfonate, said propylene polymer having a molecular weight of from about to about 5000.

2. A non-aqueous lubricant composition comprising a major proportion of a hydrocarbon oil and in combination therewith from about 0.001 to about 10% of a potassium-containing neutralized reaction product of P285 and a butyiene polymer having a molecular weight of from about 500 to about 10,000 obtained by reacting said polymer with from about 1% to about 50% P235 at a temperature of from about 200 F. to about 500 F. and neutralizing the resultant reaction product with a potassium-containing basic reagent, and from about 0.01% to about 10% of a potassium salt of a polybutene alklated benzene sulfonate, said polybutene having a molecular weight of from about 100 to about 5000.

3. A non-aqueous lubricant composition consisting essentially of a major proportion of a hydrocarbon oil, from about 0.001% to about 10% of an alkali metal-containing neutralized reaction product of a phosphorus sulfide and a polymer of a mono-olefin having less than 6 carbon atoms, said polymer having a molecular weight of from about 500 to about 10,000, said reaction product being obtained by reacting 1% to about 50% of a phosphorus sulfide with said olefin polymer at a temperatur of from about 200 F. to about 500 F., and neutralizing the resultant reaction product with an alkali metal 1. The composition described in claim 3 in which the alkali metal is potassium.

5. The composition of claim 3.in which the alkali metal is sodium.

6. The composition of claim 3 in which the olefin polymer reacted. with the phosphorus sulfide is a proplyene polymer.

7. The composition of claim 3 in which the olefin polymer reacted with the phosphorus sulfide is a butylene polymer.

8. The composition of claim 3 in which the sulfonated olefin polymer is a sulfonated propylene polymer.

9. The composition of claim 3 in which the sulfonated olefin polymer is a sulfonated butylene polymer.

10. A non-aqueous lubricant composition con sisting essentially of a major proportion of a hydrocarbon oil, from about 0.01% to about 10% of a potassium-containing neutralized reaction product of P235 and a butylene polymer having a molecular weight of about 1000, said reaction product being obtained b reacting 1 285 with said butylene polymer at a temperature of from about 200 F. to about 500 F., and neutralizing the reaction product With a basic potassium compound, and from about 0.01% to about 10% of a potassium salt of a propylene polymer alkylated benzene sulfonate, said propylene polymer having a molecular Weight of about 630.

11. A non-aqueous lubricant composition consisting essentially of a major proportion of a hydrocarbon oil, from about 0.01% to about 10% of a potassium-containing neutralized reaction product of P2555 and a butylene polymer having a molecular Weight of about 1000, said reaction REFERENCES CETED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,232,117 Kyrides Feb. 18, 1941 2,261,047 Assefi Oct. 28, 1041 2,316,082 Loane 1 Apr. 6, 1943 2,315,090 Kelso Apr. 6, 1943 2,322,307 Neely June 22, 1943 2,369,632 Cook Feb. 13, 1945 2,375,315 Mixon May 8, 1945 2,378,820 Amott June 19, 1945 2,421,004 Berger May 27, 1947 2,450,585 DOuville Oct. 5, 1943 

1. A NON-AQUEOUS LUBRICANT COMPOSITION COMPRISING MAJOR PROPORTION OF A HYDROCARBON OIL AND IN COMBINATION THEREWITH FROM ABOUT 0.001% TO ABOUT 10% OF A POTASSIUM-CONTAINING NEUTRAL IZED REACTION PRODUCT OF P2S5 AND AN OLEFIN POLYMER HAVING A MOLECULAR WEIGHT OF FROM ABOUT 500 TO ABOUT 10,000 OBTAINED BY REACTING SAID OLEFIN POLYMER WITH FROM ABOUT 1% TO ABOUT 50% P2S5 AT A TEMPERATURE OF FROM ABOUT 200* F. TO ABOUT 500* F. AND NEUTRALIZING THE RESULTANT REACTION PRODUCT WITH A POTASSIUM-CONTAINING BASIC REAGENT, AND FROM ABOUT 0.01% TO ABOUT 10% OF A POTASSIUM SALT OF A PROPYLENE POLYMER ALKYLATED BENZENE SULFONATE, SAID PROPYLENE POLYMER HAVING A MOLECULAR WEIGHT OF FROM ABOUT 100 TO ABOUT
 5000. 